Physica 79A (1975)

447-477 0 North-Holland Publishing Co.

EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS*

JAGDISH MEHRA#
Znstituts Znternationaux de Physique et de Chimie,
1050 Brussels, Belgium

Received 16 December 1974

Synopsis
In three papers (1902-1904), Albert Einstein developed the essential principles of the statistical
mechanical approach to thermodynamics before he was twenty-five years old. Einstein’s work
was inspired by Ludwig Boltzmann’s Vorlesungen iiber Gastheorie, but it was completely indepen-
dent of J. Williard Gibbs’s (whose monograph on statistical mechanics was published in 1902).
In certain respects, especially in the search for the existence of atoms of matter and quanta of
radiation by a study of fluctuations, Einstein’s work went beyond Boltzmann’s and Gibbs’s.
For Einstein, his study of the principles of statistical thermodynamics was merely a prelude to
his achievements in quantum theory and brownian motion.

1. Introduction. Albert Einstein, at the age of 23, completed his first paper on
the statistical foundation of thermodynamics in Berne, Switzerland. It was entitled,
“Kinetische Theorie des Warmegleichgewichtes und des zweiten Hauptsatzes der
Thermodynamik” (Kinetic Theory of Thermal Equilibrium and the Second Law
of Thermodynamics). It was received by the Annalen der Physik on 26 June 1902,
and was published a few weeks laterl). This was Einstein’s third scientific paper
to be published”.
The period during which this paper was written had been very critical in Ein-
stein’s life. Since the completion of his “Diplom” studies at the Zurich Polytechnic
(the E.T.H.) in the fall of 1900, he had been constantly in search of a suitable job.
When Einstein started work on the foundations of statistical thermodynamics,

* This is an invited article on the early history of statistical mechanics.

# Present address: Ecole de Physique, Universite de Geneve, Geneva, Switzerland.
k Einstein’s first published scientific paper was: “Folgerungen aus den Capillaritltserscheinun-
gen” (ref. 2, received 16 December 1900). His second paper was on “Thermodynamische Theorie
der Potentialdifferenz zwischen Metallen und vollstandig dissoziierten Liisungen ihrer Salze und
eine elektrische Methode zur Erforschung der Molekularkrafte” (ref. 3, received 30 April 1902).
Later on Einstein called these two papers as his “worthless, beginner’s works”.

447
 448 J. MEHRA

after he had completed his second paper* concerning the molecular interactions,
he was looking forward to his first emp!oyment as a teacher in the technical school
(Technikum) in Winterthur. He held this job only from May to July, 1901.
Starting 15 September 1901, Einstein accepted a position as a junior teacher in a
boys’ school in Schaffhausen, and it was from there that the applied to the Swiss
Patent Office in Bern on 18 December 1901’).
At the end of April 1902 Einstein moved to Bern, where he took up his post
as a Technical Expert, Third Class, on 23 June 1902. Before joining this position
he earned his living by giving private lessons in physics and mathematics. In Bern
he met again Paul Winteler, his old friend from Aarau, who later on married
Einstein’s sister. Einstein made the acquaintance of Maurice Solovine with whom.
and Conrad Habicht, he started the Olympia Academy, their private discussion
group. Also on arrival in Bern he completed, just about the time he joined the
Patent Office, his first paper on the foundations of statistical mechanics, which
was published in the same year (1902) as J. Willard Gibbs’s Elementary Principles
in Statistical Mechanic.rh).

2. Mechanical explanation of the Second Law of Thermodynamics. Einstein had

deeply reflected on Ludwig Boltzmann’s lectures on gas theory7). He had con-
cluded that the statistical thermodynamics of Maxwell and Boltzmann was in-
complete. As he noted, “However great the achievements of the kinetic theory of
heat in the domain of gas theory, it (the mechanical-kinetic theory) has not been
able to provide an adequate foundation for the general theory of heat. It has not
yet been possible to derive the Second Law (of Thermodynamics) and the laws of
thermal equilibrium by the exclusive use of the equations of mechanics and
probability theory, although the theories of Maxwell and Boltzmann have come

* The essential ideas for his second paper occurred to Einstein early in 1902. In a letter to his
friend Marcel Grossmann, dated 14 April (1902) Einstein wrote: “I am now sure that my theory
of the attractive forces between atoms can be extended to gases and that the characteristic con-
stants of nearly all elements can be specified without undue difficulty.” (This letter is quoted by
Carl Seelig, in ref. 4, pp. 61-62. He assumes that this letter had been written in 1901, probably
because Einstein referred in it to his search for a position as an assistant at a university. How-
ever, he also referred to the help which he had received from Grossmann’s father for the position
at the Patent Office in Bern. Einstein had not applied for this position until December 1901.
In his letter of application, Einstein mentioned that he had seen an advertisement in the “Bundes-
blatt” of 11 December 1901. Seelig believes, therefore, that the letter to Grossmann was from
14 April 1902.)
In his letter of application to the Swiss Patent Office, dated 18 December 1901, Einstein also
noted, “In the first two months [September to November 19011 of my work at [Schaffhausen]
I wrote my doctoral thesis on a topic of the kinetic theory of gases, which I have submitted a
month ago to the Second Section of the Philosophical Faculty of the University of Zurich.”
This letter is reproduced in ref. 5, p. 41.
Thus Einstein had been thinking about the problems of the kinetic theory of gases since early
1901, but he completed his first paper on this subject only in June 1902.
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 449

close to this goal”*. Einstein declared that this goal was to fill this gap. He set
out to obtain the laws of thermal equilibrium, “an extension of the Second Law,
which is of importance for the application of thermodynamics”, and the “mathe-
matical expression for the entropy” by the sole use of “mechanical equations and
the theory of probability”.
In his first paper’) on the statistical foundations of thermodynamics, Einstein
based himself on the model which had been considered by Boltzmann, i.e., systems
with a large number of degrees of freedom satisfying the canonical equations of
dynamics. He introduced the set of systems from which the thermodynamical
properties could be derived, thereby defining the temperature and obtaining the
laws of thermal equilibrium. In his second paper’) dated January 1903, he sought
to develop more general postulates for physical systems satisfying individually
arbitrary linear equations, and to extend Liouville’s theorem to a system of
differential equations more general than the canonical equations of dynamics.
The organization of these two papers was very similar. In a third paper”), dated
Bern, 27 March 1904, Einstein returned to the definition of entropy, deriving an
expression for it analogous to that of Boltzmann and Planck. On the basis of these
considerations he discussed the formulation of the Second Law of Thermo-
dynamics. These three papers represent the highlight of Einstein’s contribution to
the statistical foundation of thermodynamics.

2.1. Mechanical equations for large systems. Einsteinconsideredan ar-

bitrary physical system whose state is described by the position variables pi and the
corresponding canonical-momentum variables qi . The energy E of the system con-
tains a kinetic part L and a potential part V. Being interested in the exchange of heat
between the systems, Einstein separated the potential energy into two parts : the ex-
ternal conditions, such as gravitation and the rigid walls of the enclosure, give rise to
an external potential V,, which is assumed to be constant in time; while the rapidly
fluctuating internal forces, causing the heat transfer, give rise to a potential Vi ‘.Thus,

E = L + Va + Vi(t)- (1)
* Boltzmann believed that in the probabilistic interpretation of the entropy he had found a
very general principle which did not have to be limited to the case of gases, and he had expressed
this conviction in his great paper of 1877 (ref. 8). In his Vorlesungen iiber Gastheorie (ref. 7),
however, Boltzmann distinguished between the mathematical significance of the function H (the
measure of the probability of states whose variations were obtained by the detailed analysis of
collisions between the molecules) and its physical significance in relation to the entropy. Boltz-
mann discussed this physical significance explicitly only for special cases, “so as not to make it
incomprehensible with difficulties on account of too much generality.”
In his papers, Einstein explicitly cited Boltzmann’s lectures on gas theory, and it is indeed
possible that the studies of the young Einstein were limited to these.
# It is by considering the external potential V, that Einstein proceeded to generalize the
second law of thermodynamics. In order to realize semipermeable walls, one may assume specific
external forces acting on the molecules, which can be derived from a potential. The potential V
does not enter the Lagrange equation for the momentum q,,, i.e., 9, = Z/2 (dp,!dt).
450 J. MEHRA

Einstein introduced an infinitely large number N of identical systems whose

energy content is continuously distributed between the definite values E and
E + hE which are only slightly different from each other*. In an isolated system
the energy does not depend on the time, and one may define a distribution function
V (P 1. . . . . qJ as

dN= ~(~w.,qn).fdp~ . ..&I., (2)

9

where dN denotes the number of systems whose state variables belong to the
domain g at a certain time; g being an infinitesimal domain of all the state variables
Pl, . . ..pn. 413 . ..1 q,,, which is chosen such that E (p, , . .., q,,) lies between E
and E + 6E. Einstein used Liouville’s theorem which states that y (pI, . . ., q,J
does not change with the time if one transforms the state variab!es 1~~) . . . , qII
appropriately to P, , . . . , Qn and the region g to G#. Thus,

dN = A fdp,, . . . . dq,, (3)

y’

where A denotes a quantity independent of p and q,

2.2. Temperature function and heat equilibrium. Einstein now con-

sidered sets of similar systems with equal energy, consisting of a “heat reservoir”
Z of large energy H connected with a “thermometer” o of small heat capacity 7.
Each system CJ, with state variables p, , . . . , qn is mechanically connected with a
system Z:, with state variables IJI,, . . . , xn. The total energy is E = H + ‘1;
~74 H, E, and the interaction energy between .Z and (Tis negligible compared to ~1.
An infinitesimal domain g of all the state variables p, , . . . , q,,, 17,) . . . , xn is now
assumed to be chosen such that E lies between E and E + 6E. Then the number
dN of systems whose state variables belong to the domain g is given by,

dN = Aldp,, . . . . dXn. (3a)

9

Assuming specific smoothness conditions in the energy, the distribution function y

may be written as

y = A = A’ e-2hE = A’ e-2hti e-2hH,

(41

where h, for the moment, is an arbitrary constant.

* Such systems were called “microcanonical ensembles” by Gibbs, ref. 6, ch. X.

# This is the only mechanical input in Einstein’s derivation of the laws of thermodynamics.
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 451

The set of systems in which one can relate the distribution function y to the
energy in the specific form (4) is called a “canonical ensemble”*. Thus,

dN = A’ ,f e-**” dp, , . . ., dq,, e-2hH dI7,, . .., dxn. (5)

Einstein now restricted his attention to thermometer systems o whose state

variables lie within infinitesimal boundaries p1 and p1 + dp, , . . . , q, and qn + dqn,
whereas he allowed for arbitrary values of the state variables III, . . . , xn of the
systems Z. The number of such systems is given by

dN’ = A’ e-2hv dpl, . . . , dq, je-**” dI7,, . . ., dx,,. (6)

From physical considerations he required that the thermometer G should not

influence the heat reservoir 2, i.e., the integral in eq. (6) should be independent
of the thermometer energy ~1.From this prerequisite he derived a unique form for
the function h# :

h = + w’(E)/w(E), (7)

where w(E) = J”dL7,, . . . . dx,,, and w’(E) = [dw (E)/dE] co(E) and o’(E) are
always positive, hence h is always a positive quantity.
Jf h is chosen in this way, then the integral in eq. (6) reduces to a quantity
independent of 7, and the number of systems whose variables p1 , . . . , qn lie within
the specified limits assumes the expression

dN” = A”e-**“dpl, . . ..dq.. (8)

Eq. (8) also represents the probability (if suitably normalized by N) that the state
variables of a thermometer G, connected with a heat reservoir 2, lie between
infinitesimally close limits if the state has become stationary.
The state of the thermometer is defined by eq. (8); 12represents the temperature
function, and every observable of the thermometer system CJsimply depends on it

* The name “canonical ensemble” was proposed by Gibbs, ref. 6, chs. IVff. Einstein gave
no further justification for his procedure, and did not enlarge upon the difference between
microcanonical and canonical ensembles as Gibbs did in his book.
4 Eq. (7) is derived by noting that the integral appearing in eq. (6) is a function X of (E - 7)
and 2 (E - q) z x(E) - E;c’ (E) = x(E) if x’(E) = 0. Since x(E) = eeZhE w(E), eq. (7)
follows.
The positivity of h is established with the help of a mathematical trick. For n > 2 and LY> 1
one proves that

UJ(fl, ,..., x,) = ~-*CIJ(~~, . . . . fl,,,%, I%...,%,,IJ)‘~ml,..., Ir,,xda ,..., ~tt/S),

and from this it follows that w’(E) z 0, since o(E) can be composed of the differentials dw (E)
which satisfy the above inequality such that do) (Ez) > do) (Er) if Ez > El.
452 J. MEHRA

as long as the external potential V, is not changed. The temperature function h

depends only on the heat reservoir Z, not on the details of the contact, and one
can derive the laws of temperature balance. Thus, it follows that:
(i) if a heat reservoir Z is connected with two thermometers G and G’, both show
the same temperature function h;
(ii) if one introduces only identical systems cr and calls T the observed “temperature
value”, then one can deduce the temperature function h from T, and from h the
energy of the heat reservoir connected with o;
(iii) thermal equilibrium between the systems Z, and Z2 exists only if h, = 12, or
Tl = T,;
(iv) if two mechanical systems ZI and 2, are connected with very small interaction
energy, then on separating the systems one still obtains Tl = T2 and h, = k, ;
(v) two systems with the same temperature function k can be connected without
an observable change of the state variables;
(vi) if X1 is in thermal equilibrium with A”, and Z3, then Z2 and 2, are also in
thermal equilibrium.
Einstein now looked for the mechanical significance of the quantity II’. The
kinetic energy L of the system is a homogeneous quadratic function of the quanti-
ties q. By a linear substitution of the variable Y, L assumes the form

L = $(D~~T: + a& + ..a + oI,r,2),

and

[dq,, . . . . dq, = jdr,, . . . . dr,,.

The quantities r were called the “momentoids” by Bolttmann. The average kinetic
energy per degree of freedom, or corresponding to a momentoid, from eq. (8) is
given by,

Ljrz = s A” e -*h(V+al*,Z+a,r,=+‘.‘+a,r,2) +o(,r,2,-Q, . . . dpn &., . . . d,.n

-2h(“+a~r,2+~~‘~2+...+an~“2)dp, . . . dp n &., .., d,. = l/4/?

i .bf”e n (9)

Einstein considered a gas molecule as the thermometer @, treating the heat

reservoir 2 as consisting of all the other molecules. The Maxwell distribution
then follows from eq. (8). Moreover, since a molecule has six degrees of freedom,
neglecting the internal ones, its average kinetic energy is Sk. From the kinetic
theory of gases, one knows that the average kinetic energy is proportional to the
pressure of the gas at constant volume; and the pressure, in turn, is proportional
to the absolute temperature T. Thus Einstein obtained

1/4/z = zT = &o @)/w’(E), (10)

* CJ ref. 7, part 11, sections 33, 34 and 42.

 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 453

where x is a universal constant and u denotes the function introduced earlier

[es. (711.

2.3. The second law of thermodynamics. In order to obtain the second

law of thermodynamics as a consequence of the mechanical theory, Einstein
considered a mechanical system of n degrees of freedom, having as its coordinates
the position variables pl, . . . , p,,, and their time derivatives pi = dp,/dt, , . . . , p:.
The internal potential energy of the system is Vi, and its kinetic energy L is a
homogeneous quadratic function of pi. Two kinds of external forces act on the
system. The first, P:l’, represent the constraints of the system and can be derived
from a potential V,, which is a function of the p’s only. The forces due to gravi-
tation, adiabatic walls, etc., belong to this group, and Pzl’ = aV,/ap,. Since one
is considering processes which consist, in the limit,, of a succession of stationary
states, V, may depend explicitly on the time, but the partial derivatives with
respect to time of av,/ap, (Y= 1,. . . , n) are assumed to be infinitesimally small.
The other kind of forces, P:” = Il,, c annot be derived from a potential ; they are
responsible for heat exchange.
From Lagrange’s equations one obtains,

17 = a(Vi+V,-L) +d
Y (11)
ab
The work done on the system by the forces nV in time dt represents the amount
of heat dQ transferred to the system,

or, with eq. (10)

-dQ = ..$ + 4xh+dp,, (13)

T y ap,
where V = Vi + V,.
Now consider the term XV (aV/ip,) dp,. This term is proportional to the in-
crease of the potential energy by the heat transfer, provided the total potential
depends only slowly on the time. If the variation of the temperature function h
with respect to the time is also assumed to be infinitesimal, then the summation
can be replaced by the average over many systems of equal temperatures*. Ein-

* This step involves an assumption which Einstein did not prove in his first paper, ref. 1.
It is that the “time average” of a system is related to the average over a microcanonical ensemble.
Einstein returned to the consideration of the time ensemble in his subsequent paper (ref. 8), but
there also he did not give a specific proof of the assumption involved. This assumption has to
do with Boltzmann’s “ergodic” hypothesis. This fact seemed to be so obvious to the young
454 J. MEHRA

stein then considered a very large number of stationary systems with identical
values of I7 and V, (or, rather, h lying between /z and iz + 611, V, between P’:, and
V, + SV,, and V between V and Y + SV). The number of systems whose state
variables lie within an infinitesimal domain g is then given by

dN = A ee2’*(Y+I,! {dpl ... dpn.

For given lz and V,, I/ can be chosen such that the constant A becomes unity:
and the new total potential is expressed as V*. Then.

441
i3v*
c -dp,=!$
8P”
...
dq, V:k 0 (e-2h(“*+L)).

This expression denotes the increase in the average potential energy of the system
that would occur if the state distribution were to change in accordance with S V*
and Bh, without an explicit change in V itself. Thus,

assuming that the total number of systems considered does not change, i: and i
being the average values of the potential and kinetic energies, respectively.
From eq. (9), h = n/4L, hence 6/z = -(n/4L’) 8L. From eqs. (lo), (13) and (15),
one thus obtains,

since 6 (L/T) = 8 (w) = 0 and E* = V” + L.

Thus the term E*/T determines, up to a constant, the entropy of the system,
and the second law of thermodynamics in the form of Carnot’s principle “appears
as a necessary consequence of the mechanical worid picture”*.
Moreover, E* = E + E,,, and E, is determined as a function of E and /I from
the relation,

N=le- 2’l(E-Eo) dp, .. dg,.

Einstein (whose knowledge of the kinetic theory was derived almost completely from Boltzmann’s
“Gastheorie”) that he did not find it necessary to go into further details. Boltzmann’s “ergodic”
hypothesis was first examined in detail by P. and T.Ehrenfest in their article on “The Conceptual
Foundations of Statistical Mechanics” (ref. 1I).
* Ref. 1, p. 432.
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 455

Einstein wrote the final form of the entropy as,

6 = (E/T) + 2%log (JemzhE dpl ... dq,,) + const. (17)

In eq. (17), only the first term is of physical interest, since the second term represents
a constant and the third does not depend either on E or T.
Einstein concluded, “The expression for the entropy E is noteworthy because
it depends on E and T alone, and the special form of E as the sum of potential
and kinetic energies does not enter. This fact allows us to presume that our results
are more genera1 than the mechanical formulation employed [by us], especially
since the expression for 12[eq. (IO)] exhibits the same property.” *
“Concerning the nature of the forces which correspond to the potential V,“,
Einstein continued, “nothing need be assumed, not even whether these forces exist
in nature. The mechanical theory of heat requires that we should arrive at the
correct results if we apply Carnot’s principle to idea1 processes that can be gener-
ated from the observed ones by the introduction of arbitrary V,. Naturally the
results obtained from the theoretical consideration of these processes have real
significance only when the arbitrary, auxiliary forces V, do no appear in them” ‘.

3. The foundation of thermodynamics. Einstein worked on his second paper on

the statistical basis of thermodynamics from June 1902 to January 19039). During
this time he was employed at the Swiss Patent Office in Bern. On 6 January 1903
he married Mileva Marie, his former fellow student at the E.T.H. in Zurich, and
for the first time began to feel the benefits of a well-ordered life (“bescheidenes
Familienleben”)‘. The work at the Patent Office kept him busy eight hours a
day, but Einstein used his leisure hours for scientific work, reading and discussions.
With his friends Maurice Solovine and Conrad Habicht, the other members of the
Olympia Academy, he read and discussed the works of great scientists, philo-
sophers, and writers, including Spinoza and Hume, Mach and Helmholtz, Riemann,
Dedekind and Clifford, Ampere and Poincare, Sophocles, Racine, Dickens, Cer-
vantes, and many others*.
In a letter to his friend Michele Besso, dated January 1903, Einstein wrote, “At
fast on Monday I sent away my paper, after many modifications and corrections.
Now it is completely clear and simple, and I am fully satisfied. The concepts of
temperature and entropy follow from the principle of energy conservation and
the atomistic theory. By employing the hypothesis that the state distributions of

* Ref. 1, p. 433.
* Ref. I, p. 433. By means of such a treatment one can verify the application of the second
law of thermodynamics to processes in which one assumes, for instance, the existence of semi-
permeable walls which can be realized physically only with difficulty.
: Ref. 4, p. 71.
* Ref. 4, p. 69.
 456 J. MEHRA

isolated systems never pass into those which are less probable, there follows the
second law of thermodynamics in its most general form, namely the impossibility
of a pevpetuum mobile of the second kind”r2).
What caused Einstein such satisfaction, and which improvements and additions
had he made on the substance of his previous paper on the mechanical explanation
of the second law of thermodynamics?
In his second paper Einstein attacked the problem of deriving the laws of
thermodynamics from statistical considerations more general than those used in
kinetic theory, which he had employed in his first paper.

3.1. Mechanical description of large systems. Einstein made two essen-

tial amendments to his previous treatment of the mechanical description of large
systems: 1) he did not use Liouville’s theorem explicitly, and 2) he introduced the
time ensembles.
An isolated system depends on n state variables p1 , p2, . . . , pn, and is described
at each instant by n linear differential equations,

dPi
- = pli (PI > ...- PA. (18)
dt

where the vr are given, unique functions. There exists at least one integral (dis-
regarding the others) of eqs. (18) which does not include the time, namely the
energy.
In order to define a stationary state, Einstein used the property that the variables
PI 3 ..-> p,, of the system take on the same values again and again with the same
multiplicity. The same fact can be expressed as follows: Given a domain r of the
phase space (of state variables), then the ratio of the time during which the state
lies in that domain, to the total time T, tends to a constant value in the limit,

lim z,lT = const., (19)

r+sc

which is independent of the time. This ratio is infinitesimally small for an in-
finitesimal domain of the phase space. At any arbitrary instant, the number of
systems whose state variables lie within the domain r is given by Nlim,,, t/T,
which does not depend on the arbitrarily chosen instant.
The number of systems whose state variables occupy at any time an infinitesimal
domain r of the coordinates pl, . . . , pn is given by

dN = "(~1, . ..diJdp., .... dp,,. (20)

The function F is obtained by considering the distribution in eq. (20) as stationary.

If I’ is so chosen that p1 lies between p1 and p, + dp, . . . , , pn between pn and dp,, ,
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 457

then at the time t,

dNt = ~(PI, . . ..p.)dp, dp, ... dpn. (21)

Now the procedure which Einstein used was to let the time development
determine the probability of a system in this time ensemble. For the stationary
system at time I + dt he required

’ a (a%) dp,
dN,+,, = dN, - c ~ ... dp, = dN,. (22)
v=l ap,
From this, it immediately follows that

+ y(E)
1
= const emm. (23)

Einstein then defined the new state variables 17, , . . . ,17,, and absorbed the factor
e-“’ in one of the coordinates, obtaining

dN = const JdII, e.0 dI7,,. (24)

This equation is identical with eq. (3) derived in his first paper, but the spirit of
the new derivation was completely different.

3.2. Heat equilibrium. Having obtained eq. (24) Einstein again considered
a microcanonical ensemble of systems consisting of a heat reservoir 2 (with state
variables 17, , . . . , UL) and a thermometer (T (with state variables z1 , . . . , nJ. The
energy E, constant to within dE, of a system Z + ~7can be divided into two parts,

E=H+rj, (25)

where H is the energy of Z (depending on II,) and 7 the energy of o (depending

on ni). Again, the distribution of the thermometer systems in states whose variables
lie between SZ~and zi + dn, (i = 1, . . . , Z) is given by

dN = const eVzh” dzr ... d7cI, (26)

with a positive function h of the energy, which thus determines the state of the
system rs. The absolute temperature of the whole system is defined by h which,
as before, is given by

T = 1/4hx. (27)

As before, Einstein deduced the rules of temperature equilibrium, verifying that

if o is a monatomic molecule of the gas, and Z and ideal Maxwell-Boltzmann gas,
458 J. MEHRA

then the definition of temperature in eq. (27) coincides with that of the kinetic
theory.

3.3. The second law and the entropy. In his first paper Einstein had
employed explicitly the lagrangian formulation in his derivation of the second law
[eqs. (ll)-(16)]. He again wished to obtain the most general formulation of the
second law, but without specifically using the equations of mechanics. In order
to proceed, several steps were necessary: (a) definition of infinitely slow processes;
(b) introduction of the entropy; (c)introduction of the probability of a distribution;
(d) derivation of the second law.

3.3.1. Infinitely slow processes. Einstein considered changes of stationary

states which are so slow that at each instant of time the distribution of states is
nearly stationary. The changes thus appear explicitly either in the energy E, or in
the functions Q,, according to eq. (l), or in both; however such that the differential
quotients remain small.
As specific processes, Einstein introduced adiabatic and isopycnic processes* ~
In an adiabatic process the system 1, with state variables p,, always obeys the
equations of motion (18); however, the functions Q)~themselves depend on the
state of a system 2 which influences system 1 adiabatically. In contrast, durifrg an
isopycnic process eqs. (18) are not valid for a system; however, before and after
the process, eqs. (18) with identical qy are valid. Hence, system 1 can obtain heat
from system 2 (of a different temperature) in an isopycnic process.
Every arbitrary infinitely slow process can be represented by a sequence of
infinitely slow adiabatic and isopycnic processes.

3.3.2. Entropy. The energy equation,

(28)

is valid for an adiabatic process. The heat transferred in an isopycnic process is

given by

(29)

Hence the total energy change in an arbitrary process becomes,

(30)

* Both of these processes are used in thermodynamics. Boltzmann had made extensive use of
processes in which the volume remains constant, i.e., isopycnic processes.
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 459

where the first term comes from the adiabatic change (L’s being the parameters
by which system 2 influences the system undergoing the change), and is zero for
an isopycnic change; and the second term arises from an isopycnic change [eq. (29)],
being zero for an adiabatic process.
Before and after the process the state of the system, which has been in contact
with a large system (reservoir) during the process, should be stationary. Its state
may be described by the probability of a canonical ensemble [as in eq. (8)] as

dW = ecezhE dp, ... dp n, (31)

where the constant C is determined by the normalization condition J d W = 1.

After the process, the constants in eq. (31) will have changed to

W: C-+C+dC; W’: h-+ h -t dlz. (32)

Moreover, from the normalization condition, s d W’ = I, and by subtraction one

obtains

s eC-2hE dp, a.3 dp,, dC- 2Edh - 2h$dl

>

dC-ZEdh-2h$$dj. ec-2hE dpr ... dp,,.

From eq. (33), it follows that the term within the parentheses must vanish, i.e.

dC - 2Edh - ?hxzd/! = 0.

Comparing the expression for dQ in eqs. (29) and (30), and using eq. (34), one
obtains 2h dQ = d (2hE - C), and with 1/4h = XT,

dQ/T = d [(E/T) - 21cC] = dS. (35)

dS is thus a total differential, and the entropy becomes

S = 2x (2hE - C) = (E/T) + 2x log JeezhE dp, . . . dp,, (36)

up to a constant.

3.3.3. Probability of state distributions. The probability of a state is

proportional to the number of systems dN in a domain of the phase space. For a
stationary state, the distribution should not depend on the time explicitly. For a
small domain g of the phase space we should have,

dW = const. Jdp, ... dp,,.

9
460 J. MEHRA

If the domain g is split into 1 parts such that jg, = jy2= ... jg,,then the probabil-
ities W, , . . . , W,, would also be equal: i.e.,

w, = w, ... = w, = l/l. (37)

If now, at a given instant, N systems are distributed among the domains

g, , . . . , g,, such that &I systems are in g, , .c2in g,, . . . , el in g,, then the probability
for this is given by

N
N!
w=
0 f
F1 ! s,! .‘. FI!
, (38)

and, since e,, . . . . al are large numbers,

logW=const.-$_elogf:=const-Jalog&dpr...dp,,, (39)
E=l

if I is large enough. E is given by the distribution function of a microcanonical or

time ensemble. For a stationary distribution E is constant, and the probability
from eq. (39) is a maximum. If, on the other hand, e depends on the values of pi
then the expression for log W would no longer be a maximum, because there
would always be distributions with higher probability in the infinitesimal neigh-
borhood of F (p, , . . . . p,).
In order to study the change of probability with time, Einstein introduced the
assumption that more probable distributions always follow the less probable ones;
i.e.the probability W always increases until the distribution of states becomes
constant and W a maximum.
With this assumption, at a later time t, one has,

-log E’ I -log 8, (40)

which follows from eq. (39) and the fact that the number of systems N remains
constant.

3.3.4. The second law of thermodynamics. Now Einstein considered an

isolated system consisting of cV subsystems with different temperature functions
h, and energies E, . The subsystems or, 02, . . . do not have an appreciable thermal
interaction, but they can interact with each other adiabatically. The state distri-
bution of system crl will not differ appreciably from the one that would prevail if
it were in contact with a physical system of the same temperature, and it could
therefore be represented as

dw, = eC(~)-2h(l)E(~)
jdp:” . . . dpi”,
cl
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 461

where the indices pertain to the subsystem IJ~. The probability of the distribution
of the total system among the state variables pl, . . . , p,, is given by a product of
the probabilities of distribution of the subsystems, i.e.,

dW = dW, dW, ..’ = exp 1, C, - 2/@, 1 dp, ..* dp,, (41)

tY ) 4

since the subsystems are assumed to be independent of each other. If there are N
such total systems, then their distribution function, defined by eq. (20) is given by

E=Nexp CC,-2h,E,, (42)

( Y )

and, with eq. (40), one finds

c (2h’E’ - C’) = (1/2x)($ + s; + . ..)

2 C(2hE - C) = (1/2x)(& + S, + ..a). (43)

That is, the sum of the entropies of the subsystems of an isolated system after any
arbitrary process is equal to or greater than the sum of the entropies of the sub-
systems before the process.
In order to complete the proof of the impossibility of a perpetuum mobiZe of the
second kind, Einstein considered an isolated system consisting of a heat reservoir
2’ with an infinitely large energy, an engine M, and subsystems L’, , 2Y2, . . . in
adiabatic contact with each other, all the subsystems being in a stationary state.
The energies of the subsystems ,X1, Z2, . . , are infinitely large compared to the
energy of the engine M.
Now the engine M goes through an arbitrary cyclic process during which the
state distributions of the systems Z, , .X2, . . . are changed adiabatically infinitely
slowly; i.e., the engine does the work and extracts an amount of heat Q from the
reservoir L’. At the end of the process the mutual adiabatic interaction of Z:, , Z; , . . .
will be different from that at the beginning of the process. The engine M has thus
converted heat Q into work.
What is the increase in entropy of the individual systems during this process?
The increase in the entropy of the heat reservoir, according to earlier discussion,
is -Q/T, where Tis the absolute temperature. The entropy of the systemsx, , Z2, . . .
does not change at all during the process since they undergo only an infinitely
slow adiabatic effect. The increase in the entropy S’ - S of the total system is
thus given by,

S’ - S = -Q/T. (44)
462 J. MEHRA

According to the conclusion obtained earlier, this quantity is always greater than
or equal to zero, and it follows that

Q 5 0. (45)

Eq. (45) expresses the impossibility of the existence of a perpetual motion machine
of the second kind.

4. The general molecular theory of heat. Einstein completed his third paper on
the statistical foundation of thermodynamics on 27 March 1904lO). The circum-
stances in which he1 ived were now quite pleasant. His position at the Patent
Office would become permanent later in the year*. He had gathered a circle of
friends, and Michele Besso, who would serve as Einstein’s sounding board for
new ideas for half a century, also came to Bern in 1904 and joined the Patent
Office.
In his third paper Einstein supplemented his earlier work on the statistical
foundation of thermodynamics, discussing five topics.
(i) He derived an expression for the entropy, which was analogous to Boltz-
mann’s expression obtained from the theory of ideal gases and to Planck’s expres-
sion used in the theory of heat radiation.
(ii) Einstein gave a condensed derivation of the second law of thermodynamics,
which extensively employed the concept of probability, as defined in eq. (39),
developed in his previous paper.
(iii) He discussed the meaning of the constant x (the Boltzmann constant with
a factor +) in the kinetic theory of gases. Einstein presented a numerical value for
this constant, derived from the relation between the gas constant R, and N, the
number of atoms in a gram atom.
(iv) In an attempt to obtain the general significance of the constant ;c, Einstein
discovered for himself the concept of fluctuations: it determines the fluctuation of
a thermodynamical system.
(v) Einstein was not satisfied with the fact that fluctuations in a normal thermo-
dynamical system (with a large number of degrees of freedom) are unobservably
small, a fact with which Boltzmann and Gibbs seemed to have been satisfied. In
searching for a system in which the energy fluctuations might become large, Ein-
stein turned his attention to the phenomenon of heat radiation in empty space.
In a region the dimensions of which are of the order of the wavelength of radiation,
Einstein expected energy fluctuations of the order of magnitude of the energy
itself.
In order to prove this idea, Einstein calculated the wavelength ;i,,, of the heat-
radiation spectrum with maximum energy. The energy of a cavity of volume v
and temperature T is given by the Stefan-Boltzmann law. Einstein related this

* This happened on 16 September 1904 (ref. 5, p. 54).

 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 463

energy in a rough estimate to the fluctuation of energy, and computed A,,,, as a

function of T by putting it equal to the cube root of the volume v and inserting
the value of the constant 31,derived from the kinetic theory. Both the dependence
on the temperature T and the order of magnitude of the constant in Wien’s dis-
placement law were reproduced correctly.

4.1. The second law of thermodynamics. Withthe help of eqs. (36) and
(7), Einstein derived

S = 2% Jog CO(E) + const. (46)

Now he turned his attention to a new derivation of the second law. A system which
has been in contact for a very long time with a heat reservoir of temperature To
absorbs an energy between E and E + dE with the probability [eq. (31)]:

W= Ce- E12xTo= C/ el12x(S-E:T,), (47)

which follows from eq. (46).

Now consider I heat reservoirs with the temperature TO. The probability that
the first has energy El, the second has energy E2, etc. is then given by

%3 = WI W, .a’ W, = C,C, ... C, exp $ (48)

u

The reservoirs are connected with an engine which performs a cyclic process, but
does not exchange energy with them. This means that the energy and entropy are
exchanged only between the I reservoirs, and since the total energy remains con-
stant just the entropy term in eq. (48) is relevant for further discussion.
Introducing once again the assumption that states with lesser probability never
follow states with higher probability, or

ZY 2 TO!;, (49)
where the prime denotes the later state, Einstein concluded that

cs: 2 csy, (50)

establishing the second law.

4.2. The constant it and fluctuations. Given the distribution, eq. (47)
the average kinetic energy of an atom in a system of atoms is given by

L, = +m,(Ez + Y$ + Cz)= exp [-4(x,, . . . . z,,)/2lcT,,]dxr ..a dz,

x Jd& ... dL 3~, (L? + rt + C,“) exp [-(1!2~T~)~~~+m, (E? + $ -t Cz>]

/[exp [ - 4 (xi, . . . , 2,)/2xT,,] dx, ... dz,

x j-G . . . d5, exp - (1/2xT,J c 3mA(6: + qi + Cf) = 3xTo, (51)

464 J. MEHRA

where x1, . . .) z, are the position coordinates, and E, , . . . , <,, the momentum co-
ordinates, of the y1atoms, and #J (x,, . . . , z,,j is the potential energy of the atomic
system.
Now from the kinetic theory of gases Einstein deduced that, since pc = RT,

and

22 = R/N x 1.3 X lo-l6 (cgs units), (52)

with R, the gas constant, equal to 8.31 x IO’, and N = 6.4 x 10Z3.
Einstein was not satisfied with this determination of it, because it did not
essentially go beyond what Boltzmann had done*. Given the assumption of the
molecular kinetic theory of matter, Einstein thought that he had to confer a deeper
significance on the fundamental constant x. He thereby discovered independently
a result which had by then already been included in Gibbs’s book# ; he had derived
the fluctuation equation.
For this purpose, Einstein studied a system which is connected with a heat
reservoir of temperature T. The probability for this system to take the energy E
is obtained from eq. (47), and the average energy I? can be calculated to be

i? = J’ const. E e-E’3xT co(E) dE, (53)

0

which can be written as

[(E - E) e-E~2xT w(E) dE = 0. (54)

Taking the derivative with respect to T, one obtains

ZfZ

Eq. (55) merely indicates the fact that the average value of the quantity in the
parentheses vanishes; hence

* In fact, Boltzmann did not use the constant x, nor did he give a number for it. This was
done for the first time by Planck in 1899 [M. Planck, iiber irreversible Strahlungsvorglnge,
s. Mitteilung, S.-B. Preuss. Akad. Wisr., 440-480, 18991.
i: Ref. 6, ch. 7, eq. (200).
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 465

The quantity 2 is defined as the mean-square fluctuation of the energy, and is a

measure of the stability of the system under consideration. Therefore, the Boltz-
unum-Planck-Einstein constant 2x determines the thermal stability of a system.
It is important to note that no kinematic quantity enters eq. (56)*.

4.3. Application to radiation. Einstein assumed that if the wavelength of

energy maximum of the heat radiation is comparable with the dimensions of the
cavity containing the radiation, then the energy fluctuation should be of the same
order of magnitude as the energy of the cavity. Though Einstein was well aware
that this system might not satisfy the conditions under which he had derived
eq. (56), he considered this fact as being inessential to first approximation.
In order to calculate the wavelength of the energy maximum of heat radiation,
Einstein used the equation

1 cz E= z E=, (57)

and the Stefan-Boltzmann law, giving the energy of radiation of temperature T,

filling a cavity of volume a,

i? = CuT4, (58)

where C = 7.06 x lo-l5 (cgs units) 14, ls). He obtained, using the value from
eq. (52),
2 (X/C)“” 0.42
il “IaXZ:u 113 z =-*
T T

* In pursuing the consequences of eq. (56) and the physical consequences of the quantity 2,
Einstein went beyond Boltzmann and Gibbs. Both Boltzmann and Gibbs had emphasized that
in large systems, which one has to consider, the deviation from the equilibrium value is immeasur-
ably small as soon as the system has attained equilibrium.
Thus Boltzmann had remarked: “Even in the smallest neighbourhood of the tiniest particles
suspended in a gas, the number of molecules is already so large that it seems futile to hope for
any observable deviation, even in a very small time, from the limits that the phenomena would
approach in the case of an infinite number of molecules.” (Ref. 7, English translation, p. 318.)
Gibbs had noted: “It follows that to human experience and observation with respect to such
an ensemble as we are considering . [the fluctuations] would be in general vanishing quantities,
since such experience would not be wide enough to embrace the more considerable divergencies
from the mean values, and such observation not nice enough to distinguish the ordinary
divergencies. In other words, such ensembles would appear to human observation as ensembles
of systems of uniform energy, and in which the potential and kinetic energies (supposing that
there were means of measuring these quantities separately) had each separately uniform values”.
(Ref. 6, pp. 74-75.)
Einstein, being younger and less cautious than both Boltzmann and Gibbs, and not having
their wisdom and experience, turned his attention immediately to a very controversial field of
his time, the theory of heat radiation. It is remarkable that Boltzmann, several years earlier, had
struggled with Planck and denied the fact that one could apply the concept of entropy to radiation
at all (see ref. 13). Einstein, fortunately, had no such scruples.
466 J. MEHRA

The experimental value of the constant in Wien’s displacement law was known
to be,

Both the temperature dependence and the order of magnitude of the factor in
Wien’s law came out correctly from Einstein’s general theory. Einstein concluded,
“I believe this accord cannot be attributed to chance because of the general nature
of our assumption”*.

5. Earlier work on the statistical foundation of thermodynamics. James Clerk

Maxwell, Ludwig Boltzmann and Josiah Willard Gibbs are generally regarded as
the founders of the rational mechanical basis of thermodynamics’. Indeed, it was
a sense of incompleteness in the work of Maxwell and Boltzmann, such as he knew
it, and a consequent feeling of inadequacy in the formulation of a general theory
of heat on the basis of the molecular-kinetic theory, that encouraged the young
Einstein to undertake the statistical-mechanical formulation of thermodynamics
(see section 2). It is of interest to examine what the eminent pioneers had achieved
before Einstein wrote his three papers” g, lo) on this subject, and what Einstein
had learned from them.
Without underestimating the preparatory works and achievements of men like
D. Bernoulli, A. Kronig, and R. Clausius, Maxwell’s distribution law of velocities
is really the starting point of statistical mechanics. Maxwell published his first
considerations on the “dynamical theory of gases” in 186016). Finding this proof
unsatisfactory, he published a different proof later on for monatomic gases in
equilibriumI’). A year before his death in 1879 Maxwell, inspired by Boltzmann’s
work, returned to this subjectIs).

5.1. Ludwig Boltzmann and statistical thermodynamics. The life-

work of Ludwig Boltzmann (1844-1906) was connected with the statistical
foundations of thermodynamics. Out of 139 papers reprinted in his collected works,
a majority, both in content and the number of pages, were devoted to that sub-
jectlg). Boltzmann, at the age of twenty-two, started his studies on statistical
thermodynamics with a paper on “the mechanical interpretation of the second
law”20). Two years later, in 1868, he generalized Maxwell’s distribution law by
including external forces, like gravity, and treating molecules consisting of several

* Ref. 10, p. 362. One cannot, however, take this numerical agreement too seriously, because
x appears as a cube-root in eq. (59) and, therefore, A,,, does not depend very critically on 1~.
However, for Einstein, this success became the starting point of the ideas which led to his paper
on the light quantum in 1905.
* The phrase “the rational foundation of thermodynamics” was used by J. W.Gibbs as the
subtitle of his monograph on the “Elementary Principles in Statistical Mechanics”, ref. 6.
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 467

atoms. Boltzmann began a series of new and fundamental studies in 1871 with a
paper on “the heat equilibrium between polyatomic gas molecules”, in which he
introduced his theory of time ensembles22), and gave in a following paper “an
analytical proof of the second law” based on the law of equilibrium of kinetic
energy. We shall return to the latter paper, because the “proof” of the second law
that Einstein gave was very similar to Boltzmann’s.
Boltzmann continued his studies on the thermal equilibrium of gases, elaborating
the “Stosszahlansatz”, and introducing the famous function H (which he denoted
by E) related to the entropy in 187224). There he proved that the distribution
“after a very long time must tend to the maxwellian” (see ref. 24 and ref. 19, vol. I,
p. 345), and also introduced his probability method for the first time, which he
would use frequently later on (as would Planck for the derivation of his radiation
formula) : the replacement of the entropy integral by a sum. Boltzmann also stated
there his theory of time ensembles more clearly.
Boltzmann returned to the statistical mechanics of gases in 1875”* ‘h). He
considered various problems of the mechanical theory of heat in 1877, and an-
swered Loschmidt’s objections concerning his mechanical derivation of the second
law, the so-called “reversibility paradox” [“Umkehreinwand”, as it was called by
Ehrenfest]27). Also in 1877, Boltzmann again discussed the relation between the
second law, the theory of probability, and the laws of thermal equilibrium2*).
There he stated clearly the proportionality between entropy and the “measure of
permutability”29).
In a review of Maxwell’s paper, “On Boltzmann’s theorem concerning the
average distribution of the kinetic energy in a system of material points”3g),
Boltzmann made a clear distinction between his own point of view and Maxwell’s :
“There is a difference in the points of view of Maxwell and Boltzmann, in so far
as the former characterizes the probability of a state by the time during which the
system occupies this state on the average, whereas the latter assumes infinitely
many identical systems with all possible initial states. The proportion of the number
of systems which have a [particular] state in relation to the total number of systems
determines the probability in question”3 ‘).
During the following years many applications of Boltzmann’s ideas can be
found in his papers. He returned to fundamental questions again in 1887,
supplementing the proof of the second law which he had given in 187132* 33).
Another study, which is particularly important in the present context, was Boltz-
mann’s paper with G. H. Bryan in 1894 entitled, “On the mechanical analogy for
the thermal equilibrium of two bodies in contact”34).
In three papers during 1896-1897 Boltzmann took up the questions raised by
E.Zermelo, i.e., can one really derive the second law of thermodynamics from a
mechanics which is fully time invariant? Boltzmann noted that the singular initial
states which do not approach the Maxwell distribution are very small in number
compared to those that do. Consequently there is no difficulty in explaining
468 J. MEHRA

irreversible processes by means of the kinetic theory. According to the molecular-

kinetic view, the second law of thermodynamics is merely a theorem of probability
theory. “The fact that we never observe exceptions does not prove that the statistical
viewpoint is wrong, because the theory predicts that the probability of an ex-
ception is practically zero when the number of molecules is large”36). Boltzmann
further argued that the second law of thermodynamics is derived from the fact
that a less probable initial state goes into a more probable final state3’). As for
the recurrence of the initial state of the system (the so-called “Wiederkehrein-
wand”, according to Ehrenfest, or “recurrence paradox”), which Zermelo had
pointed out on the basis of Poincare’s recurrence theorem, Boltzmann argued
that the time to accomplish this was very very long*j8).
It is remarkable that Boltzmann did not fully appreciate the application of his
statistical concepts to the theory of heat radiation. He had considered this subject
in 1884 in a paper on the relationship between heat radiation and the second law
without reaching a definite conclusion39). When Max Planck undertook the study
of irreversible radiative processes40), Boltzmann denied that Plan&s expression
for the entropy of radiation was the correct one”‘). Boltzmann insisted that the
increase of entropy has to do with considerations of probability, but it is not an
absolute law42). He further denied that Planck could really prove the irreversibility
of radiative processes43).
In one of his final studies dealing with the principles of statistical mechanics,
Boltzmann constructed the H curve for a simple example of probability theory44).
He drew the conclusion that both universes are possible in which the entropy
increases (a system goes from a well-ordered state to a disordered one) and
decreases. “There is no doubt that it is just as well possible to conceive a world in
which all natural processes proceed in the opposite direction of time. However,
a being in this opposite world would not experience anything different than we do.
He will denote as the past what we call future, and vice vemz"45).
As we shall see, some of the proofs given by Einstein were contained more or
less explicitly in the papers of Boltzmann, there being a difference of interpretation
here and there between certain aspects of Boltzmann’s work and Einstein’s first
two papers on statistical thermodynamics. In some respects, Einstein’s work was
closer to Gibbs’ ideas, which we shall discuss next. Of course, Boltzmann thought
more deeply about the foundations of statistical mechanics than either Gibbs or
Einstein when he treated the time ensemble and the ergodic hypothesis; also,
Boltzmann’s collision equation (Stosszahlansatz), which opened a wide field of
research in the succeeding decades, had no counterpart in the work of Gibbs or
Einstein.

* Ernest Zermelo was a German mathematician who had been a pupil of Max Planck. He
wrote very sharply against Boltzmann. Professor G.E.Uhlenbeck once told me that he had
heard from Ehrenfest that Boltzmann always referred to Zermelo as “Dieser Halunke” (rogue
or villain).
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 469

5.2. J. Willard Gibbs and statistical mechanics. With his monograph

on Elementary Principles in Statistical Mechanics, “developed with special
reference to the rational foundations of thermodynamics”, Gibbs made his im-
mortal contribution to the statistical foundation of thermodynamicP). He
recognized Clausius, Maxwell, and Boltzmann as the “principal founders” of
that branch of mechanics which seeks “to explain the laws of thermodynamics
on mechanical principles”. Gibbs is generally accepted as the founder of ensemble
theory, though Boltzmann in 1871 was the first to consider explicitly a great
number of systems and their distribution in phase, and the permanence or alter-
ation of this distribution in the course of time, and Gibbs recognized Boltzmann’s
achievements46). However, Gibbs gave the ensemble concept a much broader basis
and placed it, rather than the physical evolution of a system, at the centre of his
considerations.
After introducing Liouville’s theorem in its different versions (conservation of
density-in-phase, conservation of extension-in-phase) and applying it to the
equations of motion, Gibbs defined the mathematically most useful ensemble in
his treatment of the statistical foundation of thermodynamics: the canonical
ensemble, in which the logarithm of probability is a linear function of the temper-
ature. From the canonical ensembles he derived the laws of thermal equilibrium,
and discussed the fluctuations. Gibbs als6 introduced the microcanonical ensemble,
defined by the requirement that all systems have equal energies. He discussed the
subject of thermodynamic analogies at length, and finally treated the grand
canonica’l ensembles.
In Gibbs’s work, the equilibrium of a state is represented by the statistical
equilibrium of an ensemble. Concerning the choice of the ensemble appropriate
for a macroscopic (thermodynamic) parameter, Gibbs gave plausibility arguments.
The question as to how the equilibrium is achieved, continues to remain important
even to the present day,
With his work6), completed in December 1901, Gibbs had answered in detail
most of the questions which Einstein had in mind when he wrote his papers on the
statistical-mechanical basis of thermodynamics.

6. Boltmann, Gibbs and Einstein. 6.1. Einstein and Boltzmann. In the

opening paragraph of his first paper, Einstein referred to Maxwell and Boltz-
mann’), see section 2. He did not cite any of their specific scientific papers, and
the only reference he gave was to Boltzmann’s “Gastheorie”‘), which he had
apparently read very carefully. In his lectures on gas theory Boltzmann had
treated in detail the various problems of kinetic theory, to many of which he had
himself made decisive contributions. However, the “Gastheorie” was rather
specialized in its treatment of, and application to, gases, and the more general
statistical features which Boltzmann had treated in his papers did not have the
same prominence in his book. It was evident to Boltzmann that the world consists
470 J. MEHRA

of atoms and molecules, and if one could establish correct laws for these then they
would be valid in general. Most of his proofs had been established with gases in
mind, and were, therefore, not general enough for someone as critical and ambitious
as Einstein.
Having studied the works of Mach (ref. 4, pp. 39, 40, 69, 80, 85), Einstein was
aware of the criticism that had been levelled against the molecular-kinetic theory
of matter. Einstein looked for phenomena that would provide incontestable proof
of the existence of molecules, and it was this search that brought him to examine
the statistical foundation of thermodynamics. “My major aim in this was to find
facts which would guarantee as much as possible the existence of atoms of definite
finite size,” as Einstein recalled over four decades later4’). And, in order to pursue
this programme, he did not wish to restrict himself to systems of more or less free
gas mo!ecules.
Einstein borrowed from Boltzmann what he needed, such as the systems of
equal energy which Gibbs called “microcanonical ensembles”. He invented the
time ensemble, because no explicit remarks about it were contained in Boltzmann’s
“Gastheorie”, although Boltzmann had discussed it in his papers*. As for Ein-
stein’s derivation of the second law [ref. 1, our section (2.3)], it also had a close
similarity to Boltzmann’s derivation2”); although Einstein talked about general
systems and Boltzmann about molecules; Einstein’s proof was not more general.

6.2. Einstein and Gibbs. Gibbs’s treatise6) on statistical mechanics had

only recently appeared (1902), as one of the books published by the Yale University
Press to commemorate the bicentennial of Yale College, and Einstein was not
aware of it at that time. Its German translation, by E. Zermelo, was published only
in 190548). Although Gibbs’s book was highly formal and did not go in its physical
contents beyond the facts already known from Boltzmann’s “Gastheorie”, it
nevertheless completed the edifice of Boltzmann’s thought and put it on a rigorous
basis.
Gibbs had clearly expressed Boltzmann’s credo, making it the essence of the
rational foundation he sought to develop: “The laws of thermodynamics, as
empirically determined, express the approximate and probable behavior of systems

* Boltzmann had introduced the time ensemble explicitly in 1871, ref. 23 (or ref. 19, vol. I,
p. 288): “If we keep the external conditions (temperature, external forces), to which the body is
subject, unchanged during a very long time T, and let t denote a fraction of T during which its
state variables x1, JJ~, .,z,, ol, .... co,, lie between the limits x1 and x1 + dxl, y, and
~1 + dy, . . . . o, and CO, + dw,, then the ratio r/T is the period during which the state of the
body lies on the average between the limits indicated.” In a previous paper (ref. 46, or ref. 19,
vol. I, pp. 259-287, 282), he had calculated this time to be

dt = e-“v dxl ... do,./SS eWhm dx, ... dw,,

where h is the temperature function, as defined by Einstein in eq. (26).

 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 471

of a great number of particles, or more precisely, they express the laws of mechanics
for such systems as they appear to beings who have not the fineness of perception
to enable them to appreciate quantities of the order of magnitude of those which
relate to single particles, and who cannot repeat their e,!periments often enough
to obtain any but the most probable results” [ref. 6, p. (viii)].
This means that for systems of many particles or large number of degrees of
freedom, one can only measure an average, or “expectation” value. How does one
relate an observed value to a calculated value? Actually there are two questions
here: (i) Given a macroscopic parameter of a system, which statistical ensemble
should one choose in order to account for it? (ii) How should one define a macro-
scopic measurement?
The problem is, however, not solved if one defines, on an a priori basis, certain
ensembles which are easy to handle. This is exactly what Gibbs did in his book.
He defined the canonical ensemble as a (mathematically) practical tool for handling
questions of equilibrium thermodynamics. Gibbs both treated the microcanonical
ensemble, the system preferred by Boltzmann, and also referred to the time
ensemble*.
Gibbs had written a classic, both in form and content, which attracts the reader
even today for its Dirac-like economy of style, its appeal to rigour and abstraction,
and in its day presented a contrast to the labyrinthine vastness of Boltzmann’s
original memoirs.
Einstein’s attempt to construct a statistical basis for the laws of thermodynamics
did not arouse any interest at the time, and was almost forgotten later on in view
of his other great achievements. Einstein was a young researcher still unknown,
while Gibbs was a celebrated master of thermodynamics and mathematical
physics. Even in 1911, when Einstein was famous for his work on quantum
theory, relativity, and brownian motion, the review4g) of the conceptual foundations
of the statistical approach in mechanics by Paul and Tatiana Ehrenfest made only
a passing reference to Einstein’s work on statistical thermodynamics, considering
it as being “related to Gibbs’s treatment”.
The kinship in the approaches of Gibbs and Einstein was remarkable. Both had
proceeded from the common source of Boltzmann’s achievements, and both
sought to attain the greatest generality. For specific results, Einstein also employed
canonical ensembles. The detailed analysis of molecular collisions had played an
important role in Boltzmann’s work; of this, there was no trace in the work of
Gibbs or Einstein50).
In his work Gibbs renounced all hypotheses dealing with the detailed structure
of matter. “One is building on an insecure foundation, who rests his work on
hypotheses concerning the structure of matter,” he wrote (ref. 6, ch. X). Instead
he limited himself only to the statistical-mechanical interpretation of thermo-
dynamics. In this sense, Einstein’s point of departure and treatment were bolder.
* See ref. 6, ch. XII, Dover edition, in particular p. 142.
472 J. MEHRA

He did not doubt the possibility of obtaining from the statistical method some
proof of the reality of the existence of atoms and molecules. Einstein was also
concerned about associating entropy to probability in practice, thereby giving it
a really statistical character.
Gibbs had had years of preparation for writing a classical treatise. The young,
inexperienced, and inestablished Einstein had packed the essence of the new
statistical foundation of thermodynamics in two short papers’s9) at a difficult time
in his life, working without the benefit of participation in the atmosphere in which
science is normally pursued. Einstein had built upon Boltzmann, surpassing him
in generality at points, and “anticipated” Gibbs. In his third paperlo) of 1904,
Einstein went beyond both Gibbs and Boltzmann in looking for an observable
effect in nature due to fluctuations, thereby seeking to establish the validity of the
molecular-kinetic theory of matter. “I have discovered,” he wrote to his friend
Conrad Habicht on 14 April 1904, “in the simplest possible way the relationship
between the size of the elementary quanta of matter and the wavelengths of
radiation.” (ref. 4, p. 74). This bespoke the originality of Einstein’s insights, of
which he was to give ample proof in short order.
6.3. Paul Hertz’s criticism. In 1910 Paul Hertz, then a “Privatdozent” at
the University of Heidelberg, published two papers in the Annalen der Physik in
which he reviewed the contributions of Gibbs and Einstein to the mechanical
foundations of thermodynamics5’). Hertz himself attempted to derive the second
law of thermodynamics by seeking to generalize the methods of Gibbs and Einstein.
Hertz took issue with Einstein concerning certain points in the treatment of
thermal equilibrium in his first paperr). Einstein had concluded that: (i) if two
bodies have the same temperature before contact, they will also have the same
temperature afterwards; (ii) if two bodies in contact are separated, then both will
have the same temperature as the composite body before. Hertz’s criticism was
that “Einstein tries to make these two laws plausible. However, what he actually
demonstrates cannot even be regarded as a plausibility argument, and in fact
signifies a renunciation of his own basic principles. He seeks to prove the law of
separation [of bodies] by declaring it to be probable that the gradual separation
of a body causes only a small change in its state while it [still] touches a part
[of the other body]. Nevertheless each separation means the creation of a new
mechanism, and it is not evident what connection would exist between the states,
before and after the separation, of a system which is in contact with a part of the
separated body. Similarly, it is not justified to consider the validity of the law of
contact [between bodies] as a logical consequence of the law of separation. because
the processes considered are reversible”*.
* Ref. 51, pp. 247-248. Hertz’s comments are directed to Einstein’s conclusions (iv) and (v)
in section (2.2). It is interesting to note that Boltzmann, in his paper with Bryan (ref. 34), had
used an argument similar to Einstein’s to prove the heat equilibrium between two types of
molecules. Boltzmann had, however, applied his mechanism of collisions to obtain equilibrium.
 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 473

Hertz proposed to join two systems of equal temperature, and to prove that the
combined system has the same temperature. For this, in the microcanonical
systems in question, one has only to distribute the energies appropriately. The law
of contact is, therefore, not a mechanical law, whereas the law of separation is.
Hertz also criticized Einstein’s proof of the second law [section (3.3)], in
particular his application of the assumption that more probable states follow less
probable ones, which seemed unnecessary to Hertz in connection with the ensemble
theory used by Einstein. In short, Hertz maintained that if a virtual ensemble were
assumed then there would be two probabilities, one referring to the distribution
of the systems and the other to the distribution of one system in the course of time.
Since Einstein had talked about the separation of systems, the danger was evident
that the entropy would change discontinuously.
Einstein responded to Hertz’s critique both in a personal discussion with him
and in print 52). “His [Hertz’s] remarks concerning my treatment of temperature
equilibrium are based on a misunderstanding, which arose because [my] formula-
tion was brief and not sufficiently careful.” Einstein went on to say, “I should still
mention that, in my view, the path indicated by Gibbs in his book, which consists
in proceeding directly with a canonical ensemble, is to be preferred to the one
proposed by me. Had I been familiar with Gibbs’s book at the time, I would not
at all have published those papers, and would have limited myself to the treatment
of a few points” (ref. 52, p. 176).
Einstein did not know Gibbs’s book at that time, and he has to be regarded,
together with Gibbs, as the founder of the ensemble-theoretic basis of statistical
thermodynamics.

6.4. Later development. If Einstein’s early work on statistical thermo-

dynamics was not noticed at the time, Gibbs’s brilliant work on the principles of
statistical mechanics also did not lead to any great advance for a long time. The
Gibbs-Einstein approach was developed much later, especially in relation to the
problems of equilibrium statistical mechanics, by Tolman*53). It was from Boltz-
mann’s work, especially his 1877 memoir28) in which he discussed in great general-
ity the probabilistic significance of entropy, that Einstein’s own discoveries in the
quantum theory of radiation developed.
An important aspect of the development of the foundations of statistical
mechanics was connected with Boltzmann’s ergodic hypothesis. In the language
of Gibbs, Boltzmann had introduced two types of ensembles: the microcanonical
and the time ensemble. He related the average over the microcanonical ensemble,
Ed. to the average over the time ensemble, B’, as grn = E’. In order to prove this,

* Tolman introduced the “axiom of equal a priori probabilities”, which says that equally
large areas of the phase space have equal a priori probabilities. This assumption is independent
of all other axioms, and has to be added to the laws of mechanics in order to complete the basis
of statistical mechanics.
414 J. MEHRA

Boltzmann had proposed the ergodic hypothesis: that the system, in the course
of its evolution, goes through each point in phase space consistent with its (con-
served) energy * . Paul and Tatiana Ehrenfest replaced this hypothesis with the
weaker quasiergodic hypothesis : that each trajectory approaches arbitrarily close
to every point of the energy surface in phase space4’). The strong form of the
ergodic hypothesis was disproved by Rosenthal and Plancherels3* 54)#. The first
proof of the quasiergodic hypothesis was attempted by Rosenthal”), but a more
rigorous treatment by Fermi applied only to the so-called “canonical normal
systems”56). However, Von Neumann and Birkhoff proved the equality F”’ = 2
under very general assumptions, without using the quasiergodic hypothesis5’).
All this was far afield from Boltzmann, Gibbs and Einstein’s initial consider-
ations. In 1949 Einstein, referring to his early work, simply noted, “Not acquainted
with the earlier investigations of Boltzmann and Gibbs, which had appeared earlier
and actually exhausted the subject, I developed the statistical mechanics and
molecular-kinetic theory of thermodynamics which was based on the former”47).
This self-education led immediately to Einstein’s work on brownian motion and
the quantum theory, which helped him achieve his “major aim of guaranteeing
as much as possible the existence of atoms of matter” and quanta of radiation.
His work on statistical thermodynamics had merely been a preparation for these
achievements.
In January 1954 Einstein was asked: who were the greatest men, the most
powerful thinkers whom he had known ? He answered without hesitation,
“Lorentz”. Then he added, “I never met Willard Gibbs; perhaps, had I done so,
I might have placed him beside Lorentz”” ). This homage to Gibbs was not based
on any intellectual debt.

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2) Einstein, A., Ann. Physik 4 (1901) 513.
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# The first recognition of the mathematical distinction between ergodic and quasi-ergodic
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 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 475

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476 J. MEHRA

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 EINSTEIN AND THE FOUNDATION OF STATISTICAL MECHANICS 477

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